Luminescent heterohexanuclear complexes with platinum alkynyl and silver diphosphine as components

Abstract

Reactions between the building blocks [Ag2(mu-Ph2PXPPh2)2(MeCN)2]2+ and [Pt(C[triple bond]CC6H4R-p)4]2- (R = H, CH3) afforded strongly luminescent acetylide-linked neutral heterohexanuclear complexes Pt2Ag4(mu-Ph2PNPPh2)4 (C[triple bond]CC6H4R-p)4 (R = H, 1; CH3, 2) for X = NH, but a heterotrinuclear complex cation [PtAg2(mu-PPh2CH2PPh2)2 (C[triple bond]CC6H5)2(CH3CN)2]2+ (3(2+)) for X = CH2.

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

“…The assignment of the radiative excited state(s) is uncertain but the emission seems to be characteristic of the formation of the hexanuclear central core. With reference to previous work on heteropolynuclear Pt IIcopper(i) and -silver(i) alkynyl bridging complexes [5,25,94,120,133,135,136,141,143] the strong and enhanced phosphorescence relative to the precursor is associated to the h 2 -platina alkyne [Pt-C CPh-Cu I ] entities. The emissive state is likely to derive from a 3 …”

“…Thus, each of the four M atoms is bonded to two ligands, one from each platinum unit (Pt, Pt') but exhibits three different coordination environments: M(1) is symmetrically stabilized by the electron density of two alkynyl ligands, M(2) is coordinated to two dmpz groups, while both M(3) and M(3') are bonded to one dmpz and to the p electron density of one alkynyl ligand. All the M atoms can be considered to have a linear coordination environment; for M(1), the angles C 0 -M(1)-C 00 (C 0 and C 00 being the midpoints of the two C C vectors coordinated to it) are 157.88 (3) and 174.58 (4), for M(2), the angles N(2)-M(2)-N(2') are 168.3 (2)8 (3) I [79,86,[94][95][96][97][98][99] or Au I [100][101][102][103][104] complexes. The structural details concerning the C CPh units are typical of m,h 2 (s,p) alkynyl bridging complexes.…”

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η2(π⋅⋅⋅Tl)‐Bonding Interactions

“…[55,56] In the past two decades, much has been discovered about the photoluminescence behavior of alkynylplatinum(ii) complexes, [57][58][59][60][61][62] but, in comparison, relatively little is understood about the emissive properties of heteropolynuclear platinum systems containing alkynyl bridging ligands. [63][64][65][66] Recent studies by us [67][68][69][70] and others [63,66] 8 ] by sandwiching naked Tl I centers through Tl I -alkyne interactions, [71] thus indicating that in these systems the Tl I centers have a stronger preference for the electron-rich alkynyl entities than for the basic Pt II center. Surprisingly, in similar reactions with heteroleptic cis-or transplatinate systems [Pt(C 6 F 5 ) 2 (CCR) 2 ] 2À (R = tBu, Ph), the platinum center has a higher affinity for thallium than for the alkynyl ligands, yielding six-coordinate platinum entities with two direct PtÀTl bonds that dimerize ([{trans,cis,cisPtTl 2 (C 6 F 5 ) 2 (CCPh) 2 } 2 ]) [72] or polymerize ([{trans,trans, trans-PtTl 2 (C 6 F 5 ) 2 (CCtBu) 2 } n ]), [73] in these cases through secondary Tl I Àalkynyl(C-a) contacts.…”

A temperature-sensitive luminescent Ag20 nanocluster templated by carbonate in situ generated from atmospheric CO2 fixation

“…Recently, increasing attention has been attracted by the highnuclearity metal clusters not only because of their structures aesthetics, [1][2][3][4][5] but also owing to their intriguing properties and potential technological applications. 6,7 The preparation of high-nuclearity Ag clusters usually involves the intricate assembly of multi-components, which makes it difficult to control the formation process of a cluster that contains specific numbers of metal centres. On the other hand, anion-templated synthesis has been found to be an important niche in inducing the formation of high-nuclearity clusters.…”